An agrochemical formulation comprising crystalline form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

Abstract

The present invention relates to a pesticidal formulation containing crystalline form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of [Chemical Formula 1] TIFF2025519412000024.tif59157, and its use in plant protection applications. 【Chemical Formula 1】 TIFF2025519412000024.tif59157

Description

Technical Field

[0001] Summary of the Invention The present invention relates to a novel pesticidal formulation comprising a novel crystalline form of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1) in polymorphic form A,

Chemical Formula

[0002] its preparation method, and the novel crystalline form itself, as well as its use for the manufacture of pesticidal formulations and its use in plant protection applications, in particular its use as an insecticide.

Background Art

[0003] The compound of formula (I) having the common name flupyradifurone and the IUPAC name 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one and its production method are known from International Publication No. WO2007 / 115644. Its production method is also known from International Publication No. WO2009 / 036899.

[0004] The amorphous and crystalline forms of the compound of formula (I) are already known from International Publication No. WO2011 / 051151. The crystalline form disclosed in International Publication No. WO2011 / 051151 is marked as being thermodynamically stable therein, and its X-ray powder diffraction pattern has characteristic signals at 25°C and uses Cu-Kα radiation (1.540598 Å) with at least three of the following 2Θ (two-theta) values:

Table 1

[0005] The crystalline form disclosed in International Publication No. WO2011 / 051151 is polymorphic form B.

[0006] Background Polymorphism is the ability of a compound to crystallize in different crystal phases with different arrangements and / or conformations of the molecules in the crystal lattice. Thus, polymorphs are different crystalline forms of the same pure compound. Due to the different arrangements and / or conformations of the molecules, polymorphs exhibit different physical, chemical, and biological properties. Properties that can be affected include, but are not limited to, solubility, dissolution rate, stability, optical, and mechanical properties. The relative stability of polymorphs depends on their free energy, i.e., the more stable polymorph has a lower free energy. Under a defined set of experimental conditions, only one polymorph has the lowest free energy. This polymorph is the thermodynamically stable form, and all other polymorphs are called metastable forms. Metastable forms are thermodynamically unstable, but nevertheless, they are forms that can be prepared, isolated, and analyzed as a result of their relatively slow conversion rates.

[0007] The occurrence of different polymorphic forms (hereinafter also referred to as polymorphs or crystal forms) of an active substance is of crucial importance for production on an industrial scale as well as for the development of formulations containing the active substance, and unwanted phase changes can lead to thickening and potential solidification of the formulation and / or large crystals, which can cause blockages in application devices, such as spray nozzles in agricultural application machinery. Thus, knowledge of the presence and properties of crystal modifications is highly relevant. Each polymorph is characterized by a specific uniform packing and arrangement of the molecules in the solid state. Nevertheless, it is generally impossible to predict whether a given compound will form polymorphs and, if so, what physical and biological properties the different polymorphs may have.

[0008] Furthermore, pseudopolymorphs called hydrates or solvates can occur. A solvate is a crystalline molecular compound in which the molecules of the crystallization solvent are incorporated into the host lattice consisting of non-solvated molecules. A hydrate is a special case of a solvate where the incorporated solvent is water. The presence of solvent molecules in the crystal lattice affects the intermolecular interactions and gives each solvate unique physical properties. Thus, solvates have their own characteristic values of internal energy, enthalpy, entropy, Gibbs free energy, and thermodynamic activity.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Brief Description of the Drawings

[0010]

Figure 1a

Figure 1b

Figure 1c

Figure 1d

Figure 2a

Figure 2b

Figure 2c

Figure 2d

SUMMARY OF THE INVENTION

MEANS FOR SOLVING THE PROBLEM

[0011] Detailed Description As pointed out above, one embodiment of the present invention relates to a novel crystalline form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one according to formula (1)

CHEMICAL FORMULA

[0012] which is hereinafter also referred to as flupyradifurone (FPF).

[0013] Surprisingly, the novel polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1) has been found to be a thermodynamically stable form and kinetically highly stable but metastable, showing improved properties compared to polymorphic form B disclosed in WO 2011 / 051151.

[0014] In particular, surprisingly, polymorphic form A has been found to have improved storage stability at high temperatures.

[0015] Furthermore, the water solubility of Form A is significantly lower than that of Form B. However, despite the lower solubility, it has surprisingly been found that the biological activity / efficacy does not decrease, particularly in the formulations according to the present invention.

[0016] The compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one contains hydrogen atoms that can be any hydrogen isotope, i.e., 1 H or 2 H (deuterium), at various positions. Thus, the compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one may not contain deuterium atoms, or may contain one or more deuterium atoms. In a preferred embodiment, the compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one contains hydrogen in its natural abundance isotope composition, i.e., deuterium at a molar ratio of about 0.015%.

[0017] Polymorphic Form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by X-ray powder diffraction based on the respective diffraction patterns recorded at 25 °C and Cu-Kα1 radiation (1.5406 Å). The polymorphic Form A according to the present invention exhibits at least 3, often at least 5, particularly at least 7, more specifically at least 10, and especially all of the reflections listed below as values: Table 1: X-ray reflections of Polymorphic Form A [Table 2]

[0018] The polymorphic Form A according to the present invention is further characterized by the X-ray powder diffraction pattern shown in Figure [1a].

[0019] In a preferred embodiment, polymorphic form A according to the present invention exhibits at least 3, particularly at least 5, more specifically at least 7, even more specifically at least 10, and especially all of the characteristic reflections having the following 2Θ values ±0.2°: 15.0; 20.1; 21.0; 22.4; 29.4; 33.1 and 33.2.

[0020] In one embodiment, polymorphic form A of the present invention exhibits characteristic reflections having at least the following 2Θ values: 21.0; 22.4 and 29.4.

[0021] In one embodiment, polymorphic form A of the present invention exhibits characteristic reflections having at least the following 2Θ values: 15.0; 20.1; 21.0; 22.4 and 29.4.

[0022] In one embodiment, polymorphic form A of the present invention exhibits characteristic reflections having at least the following 2Θ values: 15.0; 20.1; 21.0; 22.4; 29.4; 33.1 and 33.2.

[0023] Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy based on each spectrum recorded at 25 °C with a laser wavelength of 1064 nm and a resolution of 2 cm. Polymorphic form A according to the present invention exhibits at least 3, often at least 5, particularly at least 7, and especially all of the bands having the following maximum peaks: Table 2: Raman bands of form A [Table 3]

[0024] TIFF2025519412000007.tif16158

[0025] Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by IR spectroscopy based on their respective spectra, which is recorded at 25 °C using a universal diamond ATR apparatus and a resolution of 2 cm -1 −1. Polymorphic form A according to the invention exhibits at least 3, often at least 5, in particular at least 7, in particular all of the bands listed as maximum peaks below: Table 3: IR bands of form A [Table 4]

[0026] In addition to polymorphic form A, polymorphic form B is known from WO 2011 / 051151, which is further characterized below.

[0027] Polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by X-ray powder diffraction based on their respective diffraction patterns recorded at 25 °C and Cu-Kα1 radiation (1.5406 Å). Polymorphic form B exhibits at least 3, often at least 5, in particular at least 7, more particularly at least 10, in particular all of the reflections listed as values below: Table 4: X-ray reflections of polymorphic form B [Table 5]

[0028] Polymorphic form B is further characterized by the X-ray powder diffraction pattern shown in Figure [2a].

[0029] Polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy based on their respective spectra, which is recorded at 25 °C with a laser wavelength of 1064 nm and a resolution of 2 cm -1 -1. Polymorphic form B exhibits at least 3, often at least 5, particularly at least 7, and especially all of the bands listed below as the maximum peaks: Table 5: Raman bands of form B [Table 6]

[0030] TIFF2025519412000011.tif59140

[0031] Polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by IR spectroscopy based on their respective spectra, which is recorded at 25 °C using a universal diamond ATR device and a resolution of 2 cm -1 -1. Polymorphic form B exhibits at least 3, often at least 5, particularly at least 7, and especially all of the bands listed below as the maximum peaks: Table 6: IR bands of form B [Table 7]

[0032] TIFF2025519412000013.tif16155

[0033] Embodiment for the production of Form A In another embodiment, the present invention is directed to a method for producing polymorphic form A, comprising the following steps: a) diluting and / or suspending a compound of formula (1) in a suitable solvent or solvent mixture; b) a step of adjusting the temperature between 0 and 25 °C by arbitrarily heating or cooling; and c) a step of storing the solution or slurry obtained in step b) at a temperature of 0 to 25 °C until the solvent evaporates and crystals of polymorphic form A are formed.

[0034] The chemical preparation of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one according to formula (1) is known from the prior art such as WO 2007 / 115644 or WO 2009 / 036899. Accordingly, the compound of formula (1) used in step a) can be prepared according to WO 2007 / 115644 or WO 2009 / 036899 (which is hereby incorporated by reference in its entirety).

[0035] Preferably, the chemical preparation of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one is carried out using butyronitrile as a solvent according to WO 2007 / 115644. The crystallization and filtration of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one are preferably carried out in butanol. After filtration, the resulting crystals are preferably washed with ethanol.

[0036] The compound of formula (1) in step a) can essentially be in any known form of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one. This means that 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be used in an amorphous form, or as a mixture of different polymorphic forms, or as a mixture containing an amorphous form and one or more different polymorphic forms.

[0037] It can be used to dilute and / or suspend the compound of formula (1) in step a), and a suitable solvent or solvent mixture in which the compound of formula (1) is obtained in polymorphic form A in step c) is an aromatic solvent or alcohol or ester or water, preferably any suitable solvent such as toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol or water.

[0038] The solution of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can also be prepared by transferring the reaction mixture obtained by a chemical reaction containing 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one to the solvent or solvent mixture according to the present invention, if necessary, after removing the reagents and / or by-products.

[0039] In step b), the temperature of the solution or slurry is adjusted to a temperature of 0 °C to 25 °C. This can be done by cooling or heating, or by waiting until the temperature is adjusted to room temperature (if it is between 0 °C and 25 °C).

[0040] In step c), the solution or slurry obtained in step b) is stored at a temperature of 0 to 25 °C until the solvent evaporates and crystals of polymorphic form A are formed. Preferably, polymorphic form A is isolated from the solvent or solvent mixture by allowing the solution or slurry to stand under the crystallization conditions of step c) until at least 90% by weight of the solvent or solvent mixture has evaporated.

[0041] The crystallization of polymorphic form A can be promoted or accelerated by seeding with seed crystals of form A.

[0042] The isolation of polymorphic form A from the mother liquor is carried out by general techniques known in the art, such as filtration, centrifugation or decantation.

[0043] The isolated polymorphic form A can be optionally washed with any solvent, preferably the solvent or solvent mixture used for crystallization, water, or a mixture of a solvent or solvent mixture and water. The washing step can be optionally repeated, whereby washing with water is often the final washing step. Washing is typically carried out at less than 30°C, often less than 25°C, particularly less than 20°C, and optionally at 0°C. In a further, optional step, the crystals of polymorphic form A can be dried and then supplied for further processing.

[0044] By the crystallization of the present invention, form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one is obtained in at least 85%, particularly 90%, most preferably at least 95%.

[0045] This means that, apart from other possible impurities, preferably the amount of remaining form B or amorphous form is less than 15%, particularly less than 10%, most preferably less than 5%.

[0046] The content of form A according to the present invention is analyzed by IR spectroscopy. A calibration curve is generated using PLS regression based on the calculated electronically mixed IR spectrum (mixed by a software computer in 5% steps). Using this curve, the proportional distribution of the different forms is calculated. For calibration accuracy, a 100% content of polymorphic form A is not excluded by the above representation.

[0047] Accordingly, a particular embodiment of the present invention relates to 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one consisting of at least 85%, often at least 90% or at least ≧95% of polymorphic form A.

[0048] Another alternative embodiment of the present invention is a process for the preparation of an aqueous dispersion of full pyraziflumid, by which the form of full pyraziflumid can be manipulated / controlled as a function of milling parameters. The relative amount of Form A in a mixture of Form B and Form A of full pyraziflumid can be maintained or increased depending on the milling parameters (see Table 11).

[0049] The choice of milling media during the milling process is known to affect the energy input during milling (Austin, L.G., Klimpel, R.R. and Luckie, P.T., 1984. Process engineering of size reduction: ball milling. Society of Mining Engineers of AIME), and as a result, a higher density milling media (e.g., zirconium oxide beads) results in, among other effects, an increase in the outlet temperature of the mill base and a potential decrease in the viscosity of the mill base, which directly improves the milling efficiency. Under these conditions, it was observed that the relative amount of Form A of full pyraziflumid increased from a small amount to the major component in the mixture.

[0050] In contrast, the use of a lower density milling media material (e.g., glass beads) does not affect the temperature of the milling process, and thus, within the limits of analytical detection, Form A does not increase during milling with glass beads at room temperature.

[0051] Embodiment of a pesticidal formulation having Form A In another embodiment, the present invention relates to a plant protection agent in the form of a conventional formulation (pesticide formulation) containing polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, wherein at least 85% by weight (preferably at least 90% by weight, more preferably at least 95% by weight) of the compound of formula (1) is present in its crystalline form A. The plant protection agent is targeted. Less than 15% by weight (preferably less than 10% by weight, more preferably less than 5% by weight) of the remainder includes other polymorphic forms of the compound of formula (I) such as the amorphous or crystalline forms disclosed in WO 2011 / 051151 (form B).

[0052] To avoid doubt, at least 85% by weight or at least 90% by weight or at least 95% by weight means 85 - 100% by weight or 90 - 100% by weight or 95 - 100% by weight.

[0053] Type of formulation Conventional formulations (pesticide formulations) are, for example, water-soluble liquids (SL), emulsion concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR) and capsule concentrates (CS), and further possible formulation types are described, for example, in Crop Life International and Pesticide Specifications, Manual on development and use of FAO and WHO specifications for pesticides, FAO Plant Production and Protection Papers - 173 (prepared by the FAO / WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576).

[0054] Formulations or use forms comprising adjuvants, such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or further adjuvants, such as adjuvants, are preferred. The adjuvants according to the invention are components that enhance the biological effect of the formulation without the component itself having any biological effect. Examples of adjuvants are agents that promote retention, spread, adhesion or penetration onto the leaf surface.

[0055] The compositions of the present invention can be provided to the end user as ready-to-use formulations, i.e., the compositions can be applied directly to plants or seeds by means of a suitable device such as a spraying or dusting device. Alternatively, the compositions may be provided to the end user in the form of a concentrate that must preferably be diluted with water before use.

[0056] These formulations are prepared by known methods, for example by mixing a compound of formula (I) with adjuvants such as extenders, solvents and / or solid carriers and / or other adjuvants such as surfactants. The formulations are produced in a suitable facility or during or before application.

[0057] The compositions of the present invention are solutions (e.g., aqueous solutions), emulsions, water- and oil-based suspensions, powders (e.g., wettable powders, soluble powders), dusts, pastes, granules (e.g., soluble granules, broadcast granules), suspoemulsion concentrates, natural or synthetic products impregnated with combinations of the compounds of the present invention, fertilizers, and any conventional Composition typeIt may be. The combinations of the compounds of the present invention may exist in a suspended, emulsified or dissolved form. Examples of specific preferred composition types are solutions, water-soluble concentrates (e.g., SL, LS), dispersible concentrates (DC), suspensions and suspension concentrates (e.g., SC, OD, OF, FS), emulsions (e.g., EC), emulsions (e.g., EW, EO, ES, ME, SE), capsules (e.g., CS, ZC, ZS, ZW), pastes or gels (e.g., PA, GD), wettable powders or dusts (e.g., WP, SP, WS, DP, DS), pre - mixes (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), pesticidal articles (e.g., LN), and gel formulations (e.g., GW, GF) for treating plant propagation materials such as seeds. These and further composition types are defined by the Food and Agriculture Organization of the United Nations (FAO). The overview is defined in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No.2, 7th Ed. March 2017, Croplife International.

[0058] Formulations as suspensions and suspension concentrates (e.g., SC, OD, OF, FS) are particularly preferred.

[0059] These formulations are prepared by known methods by mixing polymorphic form A of the compound of formula (I) with conventional additives such as conventional extenders, as well as solvents or diluents, colorants, wetting agents, dispersing agents, emulsifying agents, defoaming agents, preservatives, secondary thickeners, adhesives, gibberellins and water, etc.

[0060] Formulation of the present invention The formulations according to the present invention are exemplified as follows: In a preferred embodiment, the pesticidal formulation is a) Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, wherein at least 85% by weight (preferably at least 90% by weight, more preferably at least 95% by weight) of the compound of formula (1) is present in its crystalline form A, polymorphic form A comprising.

[0061] Less than 15% by weight of the remainder (preferably less than 10% by weight, more preferably less than 5% by weight) contains other polymorphic forms of the compound of formula (I), such as the amorphous or crystalline forms disclosed in WO 2011 / 051151.

[0062] To avoid doubt, at least 85% by weight or at least 90% by weight or at least 95% by weight means 85 - 100% by weight or 90 - 100% by weight or 95 - 100% by weight.

[0063] This definition applies to all references to polymorphic form A in the present invention unless otherwise explicitly indicated.

[0064] In another preferred embodiment, the formulation is a) Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, wherein at least 85% by weight (preferably at least 90% by weight, more preferably at least 95% by weight) of the compound of formula (1) is present in its crystalline form A, polymorphic form A, b) one or more dispersants, c) one or more rheology control agents (rheology modifiers), d) optionally one or more pH buffers, e) optionally one or more defoamers, f) optionally one or more biocides, g) optionally one or more antifreezes, and h) a carrier (filler) up to 1 l (liter) comprising.

[0065] In a further preferred embodiment, the formulation a) Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, wherein at least 85% by weight (preferably at least 90% by weight, more preferably at least 95% by weight) of the compound of formula (1) is present in its crystalline form A, polymorphic form A, b) One or more dispersants, c) One or more rheology control agents (rheology modifiers), d) One or more pH buffers, e) One or more defoaming agents, f) One or more biocides, g) One or more antifreezes, and h) A carrier (filler) up to 1 L (liter) is contained.

[0066] In a preferred embodiment, polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one as defined above a) is in a concentration range of 200 to 600 g / L, preferably in a concentration range of 300 to 500 g / L, and most preferably in a concentration range of 400 to 500 g / L, and is contained in the composition according to the invention.

[0067] In another preferred embodiment of the present invention, the dispersant b) is in a concentration range of 10 to 200 g / L, preferably in a concentration range of 20 to 150 g / L, more preferably in a concentration range of 40 to 100 g / L, even more preferably in a concentration range of 50 to 90 g / L, and most preferably in a concentration range of 60 to 80 g / L, is present.

[0068] In yet another embodiment of the present invention, the rheology control agent c) is in a concentration range of 0.1 to 10 g / L, and Preferably, it is in the range of 6 to 10 g / L, exists.

[0069] In one embodiment of the present invention, pH buffer d) is , in the concentration range of 0 to 1 g / L present, Preferably, the pH buffer is essential and exists in the range of 0.01 to 10 g / L.

[0070] In one embodiment of the present invention, Antifoaming agent e) exists in the concentration range of 0.1 to 2 g / L.

[0071] In one embodiment of the present invention, Biocide f) exists in the concentration range of 0.1 to 3 g / L.

[0072] In one embodiment of the present invention, Antifreeze g) exists in the concentration range of 5 to 100 g / L, preferably 10 to 100 g / L.

[0073] Preferably, the carrier (filler) according to the present invention is added up to 1 L, and more preferably, the carrier is water.

[0074] In a preferred embodiment, the formulation a) in the concentration range of 400 to 500 g / L, b) in the concentration range of 60 to 80 g / L, c) in the concentration range of 6 to 10 g / L, and h) water up to 1 L contains.

[0075] In a preferred embodiment, the formulation a) in the concentration range of 400 to 500 g / L, b) in the concentration range of 60 to 80 g / L, c) in the concentration range of 6 to 10 g / L, d) in the concentration range of 0.01 to 10 g / L, e) in the concentration range of 0.1 to 2 g / L, f) in the concentration range of 0.1 to 3 g / L, g) in a concentration range of 10 to 100 g / L, and h) water up to 1 L (liter) is included.

[0076] Further adjuvants and auxiliaries not yet listed are, as component i), adhesives, stickers and colorants, antioxidants, light stabilizers, especially UV stabilizers, other agents for improving chemical and / or physical stability and may be present as butylhydroxytoluene [3.5 - di - tert - butyl - 4 - hydroxytoluene, CAS - No. 128 - 37 - 0].

[0077] When the formulation is used as a seed coating formulation, component i) is essential.

[0078] When treating seeds, it should be noted that generally the amount of form A of the compound of formula (I) applied to the seeds and / or the amount of further additives are selected such that the germination of the seeds is not adversely affected or the resulting plants are not damaged. This must be ensured especially in the case of active compounds which may exhibit phytotoxic effects at certain application rates.

[0079] Generally, form A of the compound of formula (I) is applied to the seeds in a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art.

[0080] Form A of the compound of formula (I) can be converted into conventional seed dressing formulations, for example solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, as well as ULV formulations.

[0081] The plant protection formulation may further comprise one or more further active substances (k) selected from the group consisting of herbicides, insecticides, acaricides, fungicides, phytotoxicity reducing agents and / or plant growth regulators.

[0082] Furthermore, within the preferred ranges described in the present invention, different preferences should be understood as being combinable with each other in permutations, but in any case, the same level of preference, in particular the most preferred embodiments / preferred levels, are in each case combined with each other and are actually disclosed as such combinations.

[0083] Compositions such as those consisting only of essential components (not any arbitrary components) should likewise be considered as being disclosed.

[0084] The auxiliaries used can be substances suitable for imparting special properties, such as specific physical, technical and / or biological properties, to the formulation of the compounds of formula (I) or to the use forms prepared from these formulations (for example, pesticidal agents ready for use such as spray liquors or seed dressing products).

[0085] Dispersant b) As used herein, the term "dispersant" refers to substances known in the art for stabilizing solid colloids of the active ingredient. Dispersant is an ionic (cationic or anionic), amphoteric or non-ionic surfactant, for example, an ionic or non-ionic or amphoteric dispersant, emulsifier, foaming agent, dispersant, wetting agent, and any mixture thereof, and may include standard surfactant substances present in the formulation of the active pesticidal ingredient.

[0086] Examples of suitable anionic surfactants include - salts of polyacrylic acid - salts of polymers of mixtures of acrylic acid / acrylate esters - salts of polymers of mixtures of acrylic acid / styrene - salts of lignosulfonic acid (such as sodium lignosulfonate) - salts of phenolsulfonic acid - salts of condensation products of phenolsulfonic acid and formaldehyde - naphthalenesulfonates, - Salts of condensation products of naphthalenesulfonic acid and formaldehyde - Salts of sulfonates of condensed naphthalene or alkylnaphthalene - Sulfonates of dodecylbenzene and tridecylbenzene - Salts of sulfosuccinic acid esters or sulfosuccinic acid ester salts - Alkyl sulfates - Salts of alkyl polyethoxylated and / or polypropoxylated sulfates - Paraffin sulfonates - Salts of alkyl sulfonic acids - Salts of alkyl polyethoxylated and / or polypropoxylated sulfates - Salts of aryl sulfonates - Salts of aryl polyethoxylated and / or polypropoxylated sulfonates - Salts of aryl sulfonates - Salts of aryl polyethoxylated and / or polypropoxylated sulfonates - Salts of alkylaryl sulfates - Salts of alkylaryl polyethoxylated and / or polypropoxylated sulfates - Salts of alkylaryl sulfonates - Salts of alkylaryl polyethoxylated and / or polypropoxylated sulfonates - Salts of diphenylsulfonate and diphenyloxide sulfonate - Salts of alpha-olefin sulfonates - Sulfonates of fatty acids and oils - Salts of α-sulfonated methyl esters - Salts of taurine derivatives (preferably alkyl taurates) - Isethionates - Salts of alkyl phosphates - Salts of aryl phosphates - Salts of alkylaryl phosphates - Salts of phosphate esters of polyethoxylated and / or polypropoxylated aliphatic straight-chain or branched alcohols - Salts of phosphate esters of polyethoxylated and / or polypropoxylated aryl alcohols - Protein hydrolysates, - Lignosulfite waste liquor - Salts of polystyrene sulfonic acid - Salts of polyvinyl sulfonic acid - Carboxylates - Ether carbonylates including, but not limited to, these.

[0087] Any reference to salts in this paragraph preferably refers to the respective alkali, alkaline earth and ammonium salts.

[0088] Examples of suitable cationic surfactants include - Those containing units comprising primary, secondary, tertiary and / or quaternary amine groups, which can form part of the main polymer chain or can be carried by side-chain substituents directly linked thereto.

[0089] - Cationic polymers based on acrylamide, methacrylamide, - N-vinylpyrrolidone - Quaternized N,N-dimethylaminomethacrylate, - Diallyldimethylammonium chloride, - Quaternized vinylimidazole (3-methyl-I-vinyl-IH-imidazol-3-ium chloride) - Acrylamidopropyltrimonium chloride - Cassia hydroxypropyltrimonium chloride, - Guar hydroxypropyltrimonium chloride or 25 polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether - Starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride - Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10, Polyquaternium-11, Polyquaternium-16, Polyquaternium-22, Polyquaternium-28, Polyquaternium-43, Polyquaternium-44, Polyquaternium-46 including but not limited to these.

[0090] Examples of suitable nonionic surfactants include - Polycondensates of ethylene oxide and propylene oxide 〇 Compounds based on ethylene oxide and propylene oxide with an average molar mass of 200 to 10,000, preferably 1000 to 4000 g / mol, and a mass ratio of the polyethoxylated block of 10% to 80%.

[0091] - Polycondensates of ethylene oxide and / or propylene oxide with aliphatic alcohols 〇 Polyethylene glycol ethers of branched or straight-chain alcohols 〇 Polypropylene glycol ethers of branched or straight-chain alcohols 〇 Polycondensates of polyethylene and polypropylene glycol ethers of branched or straight-chain alcohols, whereby the polyethylene and polypropylene parts of the surfactant can be grafted adjacent to each other or scattered randomly.

[0092] 〇 Terminal group-capped and non-terminal group-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g., butoxypolyethylene-polypropylene glycol), - Polycondensates of ethylene oxide and / or propylene oxide with fatty acids 〇 Reaction products of fatty acids or fatty alcohols with ethylene oxide and / or propylene oxide - Polycondensates of ethylene oxide and / or propylene oxide with phenol, substituted phenols (preferably alkylphenols or arylphenols): for example, tristyrylphenol ethoxylate or alkylaryl polyglycol ether or nonylphenol ethoxylate - Polycondensates of ethylene oxide and / or propylene oxide with aliphatic amines - Polyoxyethylene fatty acid esters such as castor oil ethoxylate - Polyoxyethylene fatty alcohol ethers - Fatty acid esters of polyols (such as fatty acid esters of glycerol, sorbitol or sucrose), and their ethoxylates, for example esters of polyglycerol ethoxylate, or esters of ethoxylated sorbitol - Fatty acid esters of alkanolamides - Methylcellulose - Polyvinyl alcohol - Polyvinylpyrrolidone 〇 Copolymers of PVP and dimethylaminoethyl methacrylate 〇 Butylated PVP - Copolymers of polyvinyl alcohol and polyvinylpyrrolidone - Copolymers of (meth)acrylic acid and (meth)acrylic acid esters - Polyoxyalkylene amines - Polyoxyethylene alkanediols - Polyoxyethylene and / or polyoxypropylene alkynediols - Copolymers of vinyl chloride, vinyl acetate and partially hydrolyzed vinyl acetate - Modified cellulose types - Alkyl polyglucosides are included, but not limited to these.

[0093] Examples of suitable amphoteric surfactants include - Aminopropionates and iminodipropionates - Imidazoline derivatives, such as amphoacetate, amphopropionate, amphohydroxypropyl sulfonate - Betaine - sultaine - Phosphobetaine - Amine oxide are included, but are not limited thereto.

[0094] Rheology control agent c) (thickener / modifier) As used herein, the term "rheology modifier" refers to substances known in the art to stabilize the dispersion of the active ingredient by affecting the rheological properties of the dispersion.

[0095] In addition, the formulations and the use forms derived therefrom may also contain, as further auxiliaries, sticker / rheology modifiers / thickeners, such as carboxymethyl cellulose, and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or natural phospholipids, such as cephalin and lecithin and synthetic phospholipids. Further auxiliaries may be mineral and vegetable oils.

[0096] Suitable rheology modifiers, such as thickeners, are, for example, the following - Polysaccharides including xanthan gum, guar gum and hydroxyethyl cellulose. Examples are Kelzan®, Rhodopol® G and 23, Satiaxane® CX911 and Natrosol® 250 range.

[0097] - Clays including montmorillonite, bentonite, sepiolite, attapulgite, laponite, hectorite. Examples are Veegum® R, Van Gel® B, Bentone® CT, HC, EW, Pangel® M100, M200, M300, S, M, W, Attagel® 50, Laponite® RD, - Fumed and precipitated hydrophilic silica, examples are Aerosil® 200, Aerosil® 380, Sipernat® 22.

[0098] - Fumed and precipitated hydrophobic silica, examples are Aerosil® R812, Aerosil® R812S, Aerosil® R972.

[0099] - pH buffer d).

[0100] As used herein, the term "pH buffer" refers to substances known in the art that can maintain a defined pH in an aqueous solution. Examples of such buffers are listed in the CRC Handbook of Chemistry and Physics (ISBN: 1-4987-5428-7).

[0101] Acetic acid, citric acid, formic acid, phosphoric acid, sulfuric acid are preferred.

[0102] Acetic acid and citric acid are more preferred.

[0103] Most preferred is citric acid.

[0104] Antifoaming agent e) As used herein, the term "antifoaming agent" refers to substances known in the art that can prevent excessive foaming in the formulation during manufacture and / or application by the customer. Suitable defoaming performance is the performance by which the pesticide formulation can maintain the FAO limits regarding the persistence of foam, systematized in CIPAC method 47.3, throughout its service life.

[0105] Suitable antifoaming agents are all substances customarily used for this purpose in pesticide compositions.

[0106] Silicone oil and magnesium stearate are preferred.

[0107] Biocide f) As used herein, the term " Biocide " refers to substances known in the art that can prevent the growth of microorganisms / fungi in aqueous formulations.

[0108] Suitable preservatives are all substances customarily used for this purpose in this type of pesticide composition.

[0109] Suitable biocides are preservatives such as dichlorophen and benzyl alcohol hemiformal, 5-chloro-2-methyl-4-isothiazolin-3-one [CAS-No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS-No. 2682-20-4] or 1,2-benzisothiazol-3(2H)-one [CAS-No. 2634-33-5]. Examples include Preventol® D7 (Lanxess), Kathon® CG / ICP (Dow), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).

[0110] Antifreeze g) Suitable cryoprotectants and low-temperature stabilizers are, for example, propylene glycol, ethylene glycol, urea, glycerin, inorganic salts (such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate).

[0111] Carrier h): Suitable bulking agents / carriers are, for example, from the classes of water, polar and non-polar organic chemical liquids such as aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (optionally substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidone) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).

[0112] When the extender used is water, for example, it is also possible to use an organic solvent as a co-solvent. Useful liquid solvents are essentially the following: aromatic, such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffin, such as mineral oil fractions, mineral oil and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and these can be added to water.

[0113] Examples of suitable liquid extenders / carriers / solvents include, but are not limited to, water, organic solvents and combinations thereof. Examples of suitable liquid extenders / carriers / solvents include, for example, the following classes: - Aromatic and non-aromatic hydrocarbons (cyclohexane, paraffin, alkylbenzene, xylene, toluene, tetrahydronaphthalene, alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride), - Alcohols and polyols (optionally substituted, etherified and / or esterified), such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or glycol, 2-ethylhexanol), - Ethers, such as, 〇 Dioctyl ether, tetrahydrofuran, dimethyl isosorbide, solketal, cyclopentyl methyl ether, dibenzyl ether 〇 Dow's Dowanol glycol ether products, or different grades of polyethylene glycol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol monobenzyl ether), 〇 Different grades of polypropylene glycol ethers (e.g., propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monobenzyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, tripropylene glycol monobenzyl ether), 〇 Anisole, phenetole 〇 Dimethyl polyethylene glycol of different molecular weight grades, dimethyl polypropylene glycol of different molecular weight grades, - Ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, acetophenone, propiophenone), - Esters (including methylated fats and oils such as rapeseed oil methyl ester, soybean oil methyl ester, coconut oil methyl ester, 2-ethylhexyl palmitate, 2-ethylhexyl stearate), e.g., butyl propionate, pentyl propionate, methyl hexanoate, methyl octanoate, methyl decanoate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, isobornyl acetate, benzyl benzoate, butyl benzoate, isopropyl benzoate, - Di / triesters, e.g., dimethyl succinate, dimethyl glutarate, dimethyl adipate, diisopropyl adipate, dibutyl adipate, benzyl-2-ethylhexyl adipate, dimethyl 2-methyl glutarate, monoacetin, diacetin, triacetin, trimethyl citrate, triethyl citrate, triethylacetyl citrate, tributyl citrate, tributylacetyl citrate, and mixtures and blends thereof - Lactate esters, e.g., methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethylhexyl lactate - (Poly)ethers, e.g., polyethylene glycol of different molecular weight grades, polypropylene glycol of different molecular weight grades - Unsubstituted and substituted amines - Amides (e.g., dimethylformamide, or N,N-dimethyl lactamide, or N-formylmorpholine, or fatty acid amides such as N,N-dimethyldecanamide or N,N-dimethyldec-9-en-amide) and their esters, e.g., methyl 6-(dimethylamino)-2-methyl-6-oxo-hexanoate - Lactams (e.g., 2-pyrrolidone, or N-alkylpyrrolidones, e.g., N-methylpyrrolidone, or N-butylpyrrolidone, or N-octylpyrrolidone, or N-dodecylpyrrolidone, or N-methylcaprolactam, N-alkylcaprolactam) - Lactones (e.g., γ-butyrolactone, γ-valerolactone, δ-valerolactone, α-methyl-γ-butyrolactone) - Sulfones and sulfoxides (e.g., dimethyl sulfoxide), - Oils derived from plants or animals, e.g., sunflower oil, rapeseed oil, corn oil - Nitriles, e.g., linear or cyclic alkyl nitriles, especially acetonitrile, cyclohexanecarbonitrile, octanonitrile, dodecanonitrile.

[0114] - Linear and cyclic carbonates, e.g., dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and their isomers, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, glycerol carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate and octylene carbonate.

[0115] - Phosphoric acid compounds, e.g., triethyl phosphate, tributyl phosphate, triisobutyl phosphate, trioctyl phosphate, tris(2-ethylhexyl) phosphate - White mineral oil - Any mixture of the above, e.g., 〇 An ester mixture such as Rhodiasolv RPDE, 〇 A mixture of a morpholine derivative and a cyclic carbonate, e.g., Armid FMPC 〇 A mixture of dimethyl sulfoxide and an ester and / or a glycerol derivative Polar and non-polar organic chemical liquids from the above are included.

[0116] The most preferred carrier is water.

[0117] Further adjuvants and auxiliaries i) As pointed out above, the further adjuvant and auxiliary component i) may be present. It is selected from adhesives, stickers, colorants, antioxidants, light stabilizers, especially UV stabilizers, other agents that improve chemical and / or physical stability, butylhydroxytoluene [3.5-di-tert-butyl-4-hydroxytoluene, CAS-No. 128-37-0], fragrances, protective colloids, binders, penetrants, retention promoters, stabilizers, sequestering agents, complexing agents, humectants, spreading agents / wetting agents and gibberellins.

[0118] Suitable penetrants in this context are all substances that are customarily used to improve the penetration of pesticidal active compounds into plants. A penetrant is defined, with respect to the present invention, by its ability to penetrate from the (generally aqueous) application liquid and / or from a spray coating into the cuticle of the plant and thus increase the mobility of the active compound in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include alcohol alkoxylates such as coconut fatty acid ethoxylate (10) or isotridecyl ethoxylate (12), fatty acid esters such as rapeseed oil methyl ester or soybean oil methyl ester, fatty amine alkoxylates such as tallow amine ethoxylate (15), or ammonium salts and / or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate.

[0119] Examples of suitable penetration promoters include the following: - Ethoxylated linear and / or branched fatty alcohols having 2 to 20 EO units (e.g., Genapol® X-type from Clariant); - Methyl-capped ethoxylated linear and / or branched fatty alcohols containing 2 to 20 EO units (e.g., Genapol® XM type from Clariant); - Ethoxylated coconut alcohols containing 2 to 20 EO units (e.g., Genapol® C-type from Clariant); - Ethoxylated C12 / 15 alcohols containing 2 to 20 EO units (e.g., Synperonic® A type from Croda); - Propoxy-ethoxylated alcohols, branched or linear, e.g., Antarox® B / 848 from Solvay, Atlas® G5000 from Croda, Lucramul® HOT 5902 from Levaco, Break-Thru Vibrant from Evonik; - Propoxy-ethoxylated fatty acids, Me-capped, e.g., Leofat® OC503M from Lion; - Alkyl ether citrate surfactants (e.g., Adsee CE range, Akzo Nobel); - Alkyl polysaccharides (e.g., Agnique® PG8107, PG8105 from BASF; Atplus® 438, AL-2559, AL-2575 from Croda); - Ethoxylated mono- or diesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 40 EO units (e.g., Crovol® product range from Croda); - Castor oil ethoxylates containing an average of 5 to 40 EO units (e.g., Berol® range from Nouryon, Emulsogen® EL range from Clariant); - Block copolymers of polyethylene oxide and polypropylene oxide (e.g., Pluronic range from BASF).

[0120] - Oils that function as penetration enhancers are all oils of plant, mineral, and animal origin and can be conventionally used in pesticides. Examples are: 〇 Sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil; 〇 Methyl sunflower oil, methyl rapeseed oil, methyl corn oil, methyl soybean oil, methyl rice bran oil, methyl olive oil 〇 Linear and / or branched alkyl esters of C10-C24 saturated fatty acids of plant or mineral origin: for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, 2-ethylhexyl ester of capric acid, undecylic acid, lauric acid, tridecyl acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid.

[0121] 〇 Linear and / or branched alkyl esters of C10-C24 unsaturated fatty acids of plant or mineral origin: for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, 2-ethylhexyl ester of α-linolenic acid, linoleic acid, linolenelaidic acid, palmitoleic acid, oleic acid, erucic acid.

[0122] 〇 White paraffin mineral oil, for example, Shell's Catenex (registered trademark), Exxsol (registered trademark) range.

[0123] 〇 Mixtures of two or more of the above are mentioned.

[0124] Useful retention promoters include all substances that lower the dynamic surface tension, for example, dioctyl sulfosuccinate, or all substances that increase the viscoelasticity, for example, hydroxypropyl guar polymer.

[0125] Suitable wetting agents, spreading agents and / or retention agents are, by way of example, the following: - Ethoxylated branched alcohols having 2-20 EO units (for example, Genapol (registered trademark) X type); - Methyl-capped ethoxylated branched alcohols containing 2 to 20 EO units (e.g., Genapol® XM type); - Branched or linear propoxy-ethoxylated alcohols, such as Antarox® B / 848, Atlas® G5000, Lucramul® HOT 5902; - Organo-modified polysiloxanes, such as BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwet312, Silwett® 408, Silwet® 806; - Mono- and diesters of sodium sulfosuccinate with branched or linear alcohols containing 1 to 10 carbon atoms, such as Geropon DOS; - Ethoxylated diacetylene-diols, such as Surfynol® 4xx-range; Particularly for seed treatment, colorants are often used.

[0126] Colorants that can be present in the seed coating formulations that can be used according to the present invention are all colorants that are customary for such purposes. It is possible to use either pigments that are poorly soluble in water or dyes that are soluble in water. Examples include dyes known by the names rhodamine B ([9-(2-carboxyphenyl)-6-(diethylamino)xanthen-3-ylidene]-diethylazanium; chloride), C.I. Pigment Red 112 (3-hydroxy-N-(2-methylphenyl)-4-[(2,4,5-trichlorophenyl)diazenyl]naphthalene-2-carboxamide) and C.I. Solvent Red 1 (1-[(2-methoxyphenyl)diazenyl]naphthalene-2-ol).

[0127] Useful wetting agents that may be present in the seed coating formulations that can be used according to the invention are all substances that have been conventionally used in formulations of pesticidal active compounds and that promote wetting. It is preferred to use alkylnaphthalenesulfonates, such as diisopropyl- or diisobutylnaphthalenesulfonate.

[0128] Binders that may preferably be present in the seed coating formulations that can be used according to the invention are all customary binders that can be used in seed coating products. Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, acrylics, styrene-butadiene polymers and tyroses may be mentioned as preferred.

[0129] Gibberellins that can preferably be present in the seed coating formulations that can be used according to the invention are preferably gibberellin A1, A3 (= gibberellic acid), A4 and A7; gibberellic acid is particularly preferably used. Gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- und Schaedlingsbekaempfungsmittel", vol. 2, Springer Verlag, 1970, pp. 401-412).

[0130] Further active substance k) The active compounds identified here by their common names are known and are described, for example, in The Pesticide Manual, 16th Edition, British Crop Protection Council 2012 or can be found on the Internet (for example, http: / / www.alanwood.net / pesticides). The classification is based on the current IRAC Mode of Action Classification Scheme at the time of filing of this patent application.

[0131] In one preferred embodiment, the one or more further active substances are selected from the group of insecticides / acaricides and nematicides.

[0132] Preferably selected from the following: (1) An acetylcholinesterase (AChE) inhibitor, preferably a carbamate selected from alanycarb, aldicarb, benfuracarb, benomyl, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb, or an organophosphate selected from acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, kasugamycin, chlorfenvinphos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dichlorvos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridafenthion, quinolphos, sulfotepp, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothion.

[0133] (2) A GABA-dependent chloride ion channel blocker, preferably a cyclodiene-organochlorine selected from chlordane and endosulfan, or a phenylpyrazole (fiprole) selected from ethiprole and fipronil.

[0134] (3) Sodium channel modulators, preferably acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, silafluofen [(1R)-trans isomer], deltamethrin, empenthrin [(EZ)-(1R)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, monofluorothrin, permethrin, phenothrin [(1R)-trans isomer], prallethrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R) isomer], tralomethrin and transfluthrin, or DDT or methoxychlor.

[0135] (4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, preferably neonicotinoids selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine, or sulfoximines selected from sulfoxaflor, or butenolides selected from flupyradifurone, or mesoionic compounds selected from triflumizopyrim.

[0136] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators (site I), preferably spinosyns selected from spinetoram and spinosad.

[0137] (6) Glutamate-gated chloride ion channel (GluCl) allosteric modulators, preferably abamectin, emamectin benzoate, lepimectin, and milbemectin, which are selected from abamectin / milbemycin.

[0138] (7) Juvenile hormones, preferably juvenile hormone analogs selected from hydroprene, kinoprene, and methoprene, or fenoxycarb or pyriproxyfen.

[0139] (8) Other non-specific (multi-site) inhibitors, preferably alkyl halides selected from methyl bromide and other halogenated alkyls, or chloropicrin or sulfuryl fluoride, or borax, or tartar emetic or methyl isocyanate generators selected from diazomet and metam.

[0140] (9) Chordotonal organ TRPV channel modulators, preferably pyridine azomethanes selected from pimetrozine and pyrifluquinazone, or pyropenes selected from afidopyropen.

[0141] (10) Acarid growth inhibitors that affect CHS1, selected from clofentezine, hexythiazox, diflovidazin, and etoxazole.

[0142] (11) Microorganisms that destroy the intestinal membranes of insects selected from Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B.t. plant proteins selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, and Cry34Ab1 / 35Ab1.

[0143] (12) Inhibitors of mitochondrial ATP synthase, preferably ATP inhibitors selected from diafenthuron, or azocyclotin, cyhexatin, and fenbutatin oxide, or organotin compounds selected from propargite or tetradifon.

[0144] (13) Uncouplers of oxidative phosphorylation via disruption of the proton gradient selected from chlorfenapyr, DNOC, and sulfuryl fluoride.

[0145] (14) Nicotinic acetylcholine receptor channel blockers selected from bensultap, cartap hydrochloride, thiocyclam, and thiosultap sodium.

[0146] (15) Inhibitors of chitin biosynthesis that affect CHS1, preferably benzoylureas selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron.

[0147] (16) Type 1 selected from chitin biosynthesis inhibitors and buprofezin.

[0148] (17) Molting disruptors selected from silafluofen (especially for Diptera, i.e., flies).

[0149] (18) Ecdysone receptor agonists, preferably diacylhydrazines selected from chromafenozide, halofenozide, methoxyfenozide, and tebufenozide.

[0150] (19) Octopamine receptor agonists selected from amitraz.

[0151] (20) Mitochondrial complex III electron transport inhibitors selected from hydramethylnon, acequinocyl, fluacrypyrim, and bifenazate.

[0152] (21) Mitochondrial complex I electron transport inhibitors, preferably METI acaricides and insecticides selected from phenazakine, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, and tolfenpyrad, or rotenone (derris).

[0153] (22) Voltage-dependent sodium channel blockers, preferably oxadiazines selected from indoxacarb, or semicarbazones selected from metaflumizone.

[0154] (23) Inhibitors of acetyl-CoA carboxylase, preferably tetronic acid and tetramic acid derivatives selected from spirodiclofen, spirotetramat, spirodiclofen, and spirotetramat.

[0155] (24) Mitochondrial complex IV electron transport inhibitors, preferably phosphides selected from aluminum phosphide, calcium phosphide, phosphine, and zinc phosphide, or cyanides selected from calcium cyanide, potassium cyanide, and sodium cyanide.

[0156] (25) An inhibitor of mitochondrial complex II electron transport, preferably a β-ketonitrile derivative selected from cyenopyrafen and siflumetofen, or a carboxanilide selected from piflubumide.

[0157] (28) A ryanodine receptor modulator, preferably a diamide selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole.

[0158] (29) A chordotonal organ modulator (having an undefined target site) selected from flonicamid.

[0159] (30) A GABA-dependent chloride ion channel allosteric modulator, preferably a meta-diamide selected from broflanilide, or an isoxazole selected from flupyradifurone.

[0160] (31) Baculoviruses, preferably Granuloviruses (GV) selected from Cydia pomonella GV and Thaumatotibia leucotreta (GV), or Nucleopolyhedroviruses (NPV) selected from Anticarsia gemmatalis MNPV, Flucypyriprole and Helicoverpa armigera NPV.

[0161] (32) A nicotinic acetylcholine receptor allosteric modulator (site II) selected from GS-ω / kappa HXTX-Hv1a peptide.

[0162] (33) Acrinathrin, afoxolaner, azadirachtin, benclothiaz, benzoximate, benzpyramoxan, bromopropylate, chinomethionat, chloroprallethrin, cryolite, cyclobutrifluram, cycloxaprid, cietapiprafen, cyhalodiamide, cyproflanilide (CAS 2375110-88-4), dichloromethothiaz, dicofol, dinapropylate, ε-methofluthrin, ε-momfluorothrin, flometokine, fluaazindrine, flupyrimin, fluralaner, flufenoxuron, fluopicolide, flupyradifurone, guazatine, heptafluthrin, imidaclothiaz, imidaclothiz, iprodione, isocycloseram, kappa-bifenthrin, kappa-tefluthrin, lotilaner, meperfluthrin, nylar (CAS 1771741-86-6), oxathiapiprolin, Paichongding, pyridalyl, pyrifluquinazon, pyriminostrobin, sarolaner, spidoxamat, spirodiclofen, tetramethylfluthrin, tetrachlorantraniliprole, tifolaner, thioxazafen, thiofluoximate, ticlopyrazoflor, iodomethane; further preparations based on Bacillus firmus (I-1582, Votivo) and azadirachtin (BioNeem), and the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO2006 / 043635) (CAS 885026-50-6), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-Dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]decan-3-en-2-one (known from WO2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]decan-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS 1440516-42-6), PF1364 (known from JP2010 / 018586) (CAS 1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxide-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxide-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxide-3-thietanyl)benzamide (known from WO2013 / 050317A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-(Trifluoropropyl)sulfinyl]-propanamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide (known from WO2013 / 162715A2, WO2013 / 162716A2, US2014 / 0213448A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN101337937A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN103109816A) (CAS 1232543-85-9); N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO2012 / 034403A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from WO2011 / 085575A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-(dichloropropen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN101337940A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN101715774A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylic acid ester (known from CN103524422A) (CAS 1542271-46-4); (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN102391261A) (CAS 1370358-69-2); 6-deoxy-3-O-ethyl-2,4-di-O-methyl-,1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,[[4-triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US2014 / 0275503A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 1253850-56-4), (8-anti)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 933798-27-7), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from WO2007040280A1, WO2007040282A1) (CAS 934001-66-8), N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from CN103265527A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decan-2,4-dione (known from WO2014 / 187846A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]deca-3-en-4-yl-carboxylic acid ethyl ester (known from WO2010 / 066780A1, WO2011151146A1) (CAS 1229023-00-0), N-[1-(2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO2014 / 053450A1) (CAS 1594624-87-9), N-[2-(2,6-difluorophenyl)-2H-1,2,[[3-triazol-4-yl]-2-(trifluoromethyl)benzamide (known from WO2014 / 053450A1) (CAS 1594637-65-6), N-[1-(3,5-difluoro-2-pyridinyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO2014 / 053450A1) (CAS 1594626-19-3), (3R)-3-(2-chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-diazolo[3,2-a]pyrimidinium inner salt (known from WO2018 / 177970A1) (CAS 2246757-58-2); 3-(2-chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-diazolo[3,2-a]pyrimidinium inner salt (known from WO2018 / 177970A1) (CAS 2246757-56-0); N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-2-(methylsulfonyl)-propanamide (known from WO2019 / 236274A1) (CAS 2396747-83-2), N-[2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-2-fluoro-3-[(4-fluorobenzoyl)amino]-benzamide (known from WO2019059412A1) (CAS 1207977-87-4), 3-bromo-1-(3-chloro-2-pyridinyl)-N-[4,6-dichloro-3-fluoro-2-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide (Fluchlorodiamide; known from CN110835330A, CN106977494A) (CAS:2129147-03-9).

[0163] In another preferred embodiment, the one or more additional active substances are fungicides, preferably selected from the following: 1) Ergosterol biosynthesis inhibitors, for example, (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenbuconazole, (1.005) fenhexamid, (1.006) fenpropidin, (1.007) fenpropimorph, (1.008) fenpyrazamine, (1.009) fluquinconazole, (1.010) flutriafol, (1.011) hexaconazole, (1.012) imazalil, (1.013) imazalil sulfate, (1.014) ipconazole, (1.015) ipfentrifluconazole, (1.016) menthofentrifluconazole, (1.017) metconazole, (1.018) microbutanyl, (1.019) paclobutrazol, (1.020) penconazole, (1.021) prochloraz, (1.022) propiconazole, (1.023) prothioconazole, (1.024) pyrisoxazole, (1.025) spiroxamine, (1.026) tebuconazole, (1.027) tetraconazole, (1.028) triadimenol, (1.029) tridemorph, (1.030) triticonazole, (1.031) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.032) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.033) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.034) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.035) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.(2S)-2-(1-Chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.037)(2S)-2-(1-Chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.038)(2S)-2-[4-(4-Chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.039)(R)-[3-(4-Chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.040)(S)-[3-(4-Chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.041)[3-(4-Chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.042)1-({(2R,4S)-2-[2-Chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.043)1-({(2S,4S)-2-[2-Chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.044)1-{[3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxolan-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.045)1-{[rel(2R,3R)-3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxolan-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.046)1-{[rel(2R,3S)-3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxolan-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.047) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethyl-heptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethyl-heptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.052) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.053) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.054) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.055) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.056) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.057) 2-[6-(4-Chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.058) 2-{[3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 2-{[rel(2R,3R)-3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.060) 2-{[rel(2R,3S)-3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)-oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.061) 3-[2-(1-Chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (1.062) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]-benzonitrile, (1.063) 5-(4-Chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.064) 5-(Allylsulfanyl)-1-{[3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.065) 5-(Allylsulfanyl)-1-{[rel(2R,3R)-3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.066) 5-(Allylsulfanyl)-1-{[rel(2R,3S)-3-(2-Chlorophenyl)-2-(2,4-difluoro-phenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.067) Methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propanoate, (1.068) N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.069) N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidohydroxamic acid amide, (1.070) N'-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidohydroxamic acid amide, (1.071) N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.072) N'-{5-bromo-2-methyl-6-[(1-propoxypropan-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.073) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methyl-pyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.074) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)-ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.075) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, 1.076) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.077) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.078) N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylimidohydroxamic acid amide.

[0164] 2) Inhibitors of respiratory chain complex I or II, such as, (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) cyclobutrifluram, (2.006) flubeneteram, (2.007) fluindapyr, (2.008) fluopyram, (2.009) flutolanil, (2.010) fluxapyroxad, (2.011) flutriafol, (2.012) ipfencarbazone, (2.013) isfetamid, (2.014) isoflucypram, (2.015) isopyrazam, (2.016) penflufen, (2.017) penthiopyrad, (2.018) pyriflufen-ethyl, (2.019) pyrapropisopropyl, (2.020) pyraziflumid, (2.021) sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.029) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.030) 3-(Difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.031) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.032) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.033) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.034) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide.

[0165] 3) Inhibitors of respiratory chain complex III, such as, (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) kresoxim-methyl, (3.005) cumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) fenpicoxamid, (3.012) florpicoxamid, (3.013) fluopicoxystrobin, (3.014) fluoxastrobin, (3.015) kresoxim-methyl, (3.016) mandestrobin, (3.017) metominostrobin, (3.018) methyltetraprole, (3.019) orysastrobin, (3.020) picoxystrobin, (3.021) pyraclostrobin, (3.022) pyra-metostrobin, (3.023) pyraoxystrobin, (3.024) trifloxystrobin, (3.025) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylinden]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.026) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpenta-3-enamide, (3.027) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.028) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.029) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.030) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpenta-3-enamide, (3.031) methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate.

[0166] 4) Inhibitors of mitosis and cell division, for example, (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) fluopyram, (4.006) metrafenone, (4.007) penthiopyrad, (4.008) pyridachlometyl, (4.009) pyriofenone (clazafenone), (4.010) thiabendazole, (4.011) thiophanate-methyl, (4.012) zoxamide, (4.013) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.014) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.018) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.019) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.020) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.022) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.023) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.024) 4-(2-Chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.025) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.026) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.027) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.028) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine.

[0167] 5) Compounds capable of having multi-site action, such as (5.001) Bordeaux mixture, (5.002) captan, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper sulfate (2+), (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) maneb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc, (5.017) oxine-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations (including calcium polysulfide), (5.020) thiram, (5.021) dinneb, (5.022) dithiram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3’,4’:5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

[0168] 6) Compounds capable of inducing host defense, such as, (6.001) acibenzolar-S-methyl, (6.002) fosetyl-aluminum, (6.003) fosetyl-calcium, (6.004) fosetyl-sodium, (6.005) isothianyl, (6.006) phosphorous acid and its salts, (6.007) probenazole, (6.008) thiazinyl.

[0169] 7) Inhibitors of amino acid and / or protein biosynthesis, for example, (7.001) Cyprodinil, (7.002) Kasugamycin, (7.003) Kasugamycin hydrochloride hydrate, (7.004) Oxytetracycline, (7.005) Pyrimethanil.

[0170] 8) Inhibitors of ATP production, for example, (8.001) Silthiofam.

[0171] 9) Inhibitors of cell wall synthesis, for example, (9.001) Benalaxyl-M, (9.002) Dimethomorph, (9.003) Flumorph, (9.004) Iprovalicarb, (9.005) Mandipropamid, (9.006) Pyrimorph, (9.007) Valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.

[0172] 10) Inhibitors of lipid synthesis, transport, and membrane synthesis, for example, (10.001) fluoxapiprolin, (10.002) natamycin, (10.003) oxathiapiprolin, (10.004) propamocarb, (10.005) propamocarb hydrochloride, (10.006) propamocarb fosetylate, (10.007) tolclofos-methyl, (10.008) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (10.009) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (10.010) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (10.011) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (10.012) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (10.013) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethanesulfonate, (10.014) 2-{(5S)-3-[2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (10.015) 2-{3-[2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenylmethanesulfonate, (10.016) 3-[2-(1-{[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-ylmethanesulfonate, (10.017) 9-Fluoro-3-[2-(1-{[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (10.018) 3-[2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-ylmethanesulfonate, (10.019) 3-[2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-9-fluoro-1,5-dihydro-2,4-benzodioxepin-6-ylmethanesulfonate.

[0173] 11) Inhibitors of melanin biosynthesis, for example, (11.001) tolprocarb, (11.002) tricyclazole.

[0174] 12) Inhibitors of nucleic acid synthesis, for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).

[0175] 13) Inhibitors of signal transduction, for example, (13.001) fluazinam, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.

[0176] 14) Compounds that can act as uncoupling agents, for example, (14.001) fluazinam, (14.002) meptyldinocap.

[0177] 15) Further compounds, such as (15.001) abscisic acid, (15.002) aminopyrifen, (15.003) benzthiazole, (15.004) benzoxazine, (15.005) capsimycin, (15.006) carvone, (15.007) chinomethionat, (15.008) kuffraneb, (15.009) cymoxanil, (15.010) cymoxanil, (15.011) cyprosulfamide, (15.012) diphenamidone, (15.013) flutianil, (15.014) iprobenfos, (15.015) methyl isothiocyanate, (15.016) milbemycin, (15.017) nickel dimethyldithiocarbamate, (15.018) nitrothal-isopropyl, (15.019) oxyphenisatin, (15.020) pentachlorophenol and salts, (15.021) picarbutrazox, (15.022) quinomethionate, (15.023) D-tagatose, (15.024) tebufloquin, (15.025) tecnazene, (15.026) tolylfluanid, (15.027) 2-(6-benzylpyridin-2-yl)quinazoline, (15.028) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.029) 2-phenylphenol and salts, (15.030) 4-amino-5-fluoropyrimidin-2-ol (tautomer: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.031) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.032) 5-amino-1,3,4-thiadiazole-2-thiol, (15.033) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide, (15.034) 5-fluoro-2-[(4-fluorobenzyl)oxy]-pyrimidin-4-amine, (15.035) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.036) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.037) Buta-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.038) ethyl (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.039) phenazine-1-carboxylic acid, (15.040) propyl 3,4,5-trihydroxybenzoate, (15.041) quinolin-8-ol, (15.042) quinolin-8-ol sulfate (2:1), (15.043) 1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.044) 1-(5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.045) 1-(5,6-dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.046) 1-(6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.047) 1-(6-(difluoromethyl)-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.048) 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.049) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.050) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.051) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (15.052) 3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline, (15.053) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.(054) 5-Bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline, (15.055) 8-Fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)-quinoline, (15.056) 8-Fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-quinoline, (15.057) 8-Fluoro-N-(4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl)quinoline-3-carboxamide, (15.058) 8-Fluoro-N-[(2S)-4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl]quinoline-3-carboxamide, (15.059) 9-Fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.060) N-(2,4-dimethyl-1-phenylpentan-2-yl)-8-fluoroquinoline-3-carboxamide, (15.061) N-[(2S)-2,4-dimethyl-1-phenylpentan-2-yl]-8-fluoroquinoline-3-carboxamide, (15.062) 1,1-Diethyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.063) 1,3-Dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.064) 1-[[3-Fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]azepan-2-one, (15.065) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.066) 1-Methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.067) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.068) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.069) 2,2-Difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.070) 3,3-Dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.071) 3-Ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.072) 4,4-Dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.073) 4,4-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.074) 4-[5-(Trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyldimethylcarbamate, (15.075) 5,5-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.076) 5-Methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.077) Ethyl 1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazole-4-carboxylate, (15.078) Methyl {4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate, (15.079) N-(1-Methylcyclopropyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.080) N-(2,4-Difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.(15.081) N-(2-Fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.082) N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.083) N,N-Dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.084) N-[(E)-Methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085) N-[(E)-N-Methoxy-C-methyl-carboximidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.086) N-[(Z)-Methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.087) N-[(Z)-N-Methoxy-C-methyl-carboximidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.088) N-[[2,3-Difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide, (15.089) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.090) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.091) N-{2,3-Difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.092) N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide, (15.093) N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.094) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide, (15.095) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.096) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.098) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]be. nzamide, (15.099) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene carbothioamide, (15.100) N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide.

[0178] In another preferred embodiment, said further active substance is a biopesticide.

[0179] Biopesticides include in particular bacteria, fungi, yeasts, plant extracts, and products formed by microorganisms including proteins and secondary metabolites.

[0180] Biopesticides include bacteria such as spore-forming bacteria, root-colonizing bacteria, and bacteria that act as biopesticides, fungicides or nematicides.

[0181] Examples of such bacteria that are used or can be used as biopesticides are as follows: Bacillus amyloliquefaciens, strain FZB42 (DSM 231179), or Bacillus cereus, particularly B. cereus strain CNCM I-1562 or Bacillus firmus, strain I-1582 (deposit number CNCM I-1582), or Bacillus pumilus, particularly strain GB34 (deposit number ATCC 700814) and strain QST2808 (deposit number NRRL B-30087), or Bacillus subtilis, particularly strain GB03 (deposit number ATCC SD-1397), or Bacillus subtilis strain QST713 (deposit number NRRL B-21661) or Bacillus subtilis strain OST30002 (deposit number NRRL B-50421) Bacillus thuringiensis, particularly Bacillus thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 (deposit number ATCC 1276), or Bacillus thuringiensis subsp. aizawai, particularly strain ABTS-1857 (SD-1372), or Bacillus thuringiensis subsp. kurstaki strain HD-1, or Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans, Pasteuria spp. Rotylenchulus reniformis nematode - PR3 (deposit number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD31.013, Streptomyces galbus strain AQ 6047 (deposit number NRRL 30232), Streptomyces galbus (NRRL B-50550).

[0182] Examples of fungi and yeasts that are used or can be used as biological pest control agents are as follows: Beauveria bassiana, especially strain ATCC 74040, Coniothyrium minitans, especially strain CON / M / 91-8 (deposit number DSM-9660), Lecanicillium spp, especially strain HRO LEC 12, Lecanicillium lecanii (formerly known as Verticillium lecanii), especially strain KV01, Metarhizium anisopliae, especially strain F52 (DSM3884 / ATCC 90448), Metschnikowia fructicola, especially strain NRRL Y-30752, Paecilomyces fumosoroseus (now Isaria fumosorosea), especially strain IFPC 200613, or strain Apopka 97 (deposit number ATCC 20874), Paecilomyces lilacinus, especially Paecilomyces lilacinus strain 251 (AGAL 89 / 030550), Talaromyces flavus, especially strain V117b, Trichoderma atroviride, especially strain SC1 (deposit number CBS 122089), Trichoderma harzianum, especially Trichoderma harzianum rifai T39 (deposit number CNCM I-952).

[0183] Examples of viruses that are used or can be used as biological pest control agents are as follows: Adoxophyes orana (summer fruit tortrix) granulosis virus (GV), Cydia pomonella (codling moth) granulosis virus (GV), Helicoverpa armigera (cotton bollworm) nucleopolyhedrovirus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, Spodoptera littoralis (African cotton leafworm) NPV.

[0184] Also included are bacteria and fungi that are added as "inoculants" to plants or plant parts or plant organs and that, due to their specific properties, promote plant growth and plant health. Examples that can be cited are as follows: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., particularly Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp. or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., particularly Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., Streptomyces spp. Examples of plant extracts that are used or can be used as biological pest control agents, as well as products formed by microorganisms containing proteins and secondary metabolites, are as follows: Garlic (Allium sativum), Wormwood (Artemisia absinthium), Azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, Chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up (Quinoa saponin extract), Pyrethrum / Pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem (trademark) Insecticide", Rotenone, Ryania / Ryanodine, Symphytum officinale, Tanacetum vulgare, Thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extract, in particular, rapeseed powder or mustard powder, and biocidal / acaricidal active substances obtained from olive oil, in particular, unsaturated fatty acids / carboxylic acids having a carbon chain length of C16-C20 as active ingredients, for example, those contained in a product with the trade name FLiPPER (registered trademark).

[0185] In another embodiment, the compound of formula (I) can be combined with, for example, safeners such as benoxacor, cloquintocet (-mexyl), cimmetrinil, cyprosulfamide, dichloramide, fenchlorazole (-ethyl), fenclorim, flurazole, flutoprim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

[0186] All specified mixing partners can optionally form salts with suitable bases or acids if their functional groups permit this. All named mixing partners can include tautomers where applicable.

[0187] Preferred mixing partners are selected from the group consisting of beta-cyfluthrin, deltamethrin, permethrin, transfluthrin, spirodiclofen, spidoxamat, ethiprole, fipronil, thiacloprid and tetraniliprole.

[0188] The most preferred mixing partners are deltamethrin, transfluthrin, spirodiclofen and spidoxamat.

[0189] Furthermore, the present invention relates to the use of polymorphic form A of the compound of formula (1) for controlling animal pests. "Control" means the suppression of the occurrence of animal pests (including mortality, reduction in food intake and / or disruption of mating). Surprisingly, it has been found that the systemic biological efficacy of polymorphic form A is at the same level as that of polymorphic form B, despite polymorphic form A having 60% of the water solubility of polymorphic form B.

[0190] In certain embodiments, the present invention is directed to controlling animal pests in crops of useful plants including cereals (wheat, rice, triticale, barley, rye, oats), corn, soybean, potato, sugar beet, sugar cane, tomato, pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, legumes, crucifers (such as cabbage) and other vegetable species, cotton, tobacco, rapeseed, and fruit plants (fruit apple, pear, citrus, and grape).

[0191] In particularly preferred embodiments, the useful plants are fruit and grape, vegetable and flower, coffee and cocoa (plantations), potato, cotton, cereals, sugar beet, crucifers, corn and soybean. In another specific embodiment of the present invention, the useful plants are transgenic plants.

[0192] The present invention is also directed to a method for controlling animal or microbial pests, wherein form A of the compound of formula (I) or the plant protection agent containing form A of the compound of formula (I) as defined above is allowed to act on animal or microbial pests and / or their habitats.

[0193] The control of animal pests is preferably carried out in agriculture and forestry, as well as in material protection. Preferably excluded therefrom are methods for surgical or therapeutic treatment of the human or animal body, and diagnostic methods carried out on the human or animal body.

[0194] In another embodiment, the present invention is directed to the use of form A of the compound of formula (I) for controlling animal pests. Form A of the compound of formula (I) can be advantageously used as a pest control agent, particularly in plant protection agents as described above. Preferably excluded therefrom is use in methods for surgical or therapeutic treatment of the human or animal body and in diagnostic methods carried out on the human or animal body.

[0195] For the purposes of the present application, the term "pesticide" always includes, in each case, the term "plant protection product".

[0196] All plants and plant parts can be treated according to the invention. Here, plants are to be understood as meaning desirable and undesirable wild plants and crop plants (including crop plants growing in the wild), for example cereals (wheat, rice, triticale, barley, rye, oats), maize, soybeans, potatoes, sugar beets, sugar cane, tomatoes, peppers, cucumbers, melons, carrots, watermelons, onions, lettuce, spinach, leeks, beans, crucifers (for example cabbages), other vegetable species, cotton, tobacco, oilseed rape, and fruit plants (apple fruit, pears, citrus fruits, grapes). Crop plants can be plants obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including transgenic plants, and include plant varieties that can or cannot be protected by varietal rights. Plants are to be understood as meaning all developmental stages, such as seeds, seedlings, young (immature) plants up to mature plants. Plant parts are to be understood as meaning all parts and organs of the plant above and below ground, for example shoots, leaves, flowers and roots, by way of example, leaves, needles, stems, trunks, flowers, fruiting bodies, fruits and seeds, as well as tubers, roots and rhizomes. Plant parts also include harvested plants or harvested plant parts, as well as vegetative and reproductive propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.

[0197] Treatment according to the invention of plants and plant parts in form A of the compounds of the formula (I) is carried out by customary treatment methods, for example by dipping, spraying, evaporation, atomization, scattering, coating, injection, and, in the case of propagation material, in particular in the case of seeds, by applying one or more coatings, directly or by allowing the compound to act on the surroundings, the environment or the storage space.

[0198] As already described above, according to the present invention, it is possible to treat all plants and their parts. In a preferred embodiment, wild plant species and plant varieties, or those obtained by conventional biological breeding methods such as crossing or protoplast fusion, and their parts are treated. In a more preferred embodiment, transgenic plants and plant varieties obtained by genetic engineering methods, optionally in combination with conventional methods (genetically modified organisms), and their parts are treated. The terms "part" or "plant part" or "plant parts" have been described above. The present invention is particularly preferably used for treating plants of each commercially customary cultivar or cultivar in use. Plant varieties should be understood to mean plants having new characteristics ("traits") and obtained by conventional breeding, mutagenesis or recombinant DNA techniques. They can be cultivars, varieties, biotypes or genotypes.

[0199] Transgenic plants or plant cultivars (obtained by genetic engineering) that are preferably processed according to the present invention include all plants that have received, through their genetic form, genetic material that imparts specific advantageous useful traits ("traits") to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or water or soil salinity levels, improved flowering performance, easier harvesting, accelerated ripening, higher yields of the harvested product, higher quality and / or higher nutritional value, better storage life and / or processability of the harvested product. Further examples of such traits are toxins formed in the plant, in particular toxins formed in the plant by genetic material from Bacillus thuringiensis (e.g., genes CryIA(a), CryIA(b), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb, CryIF and combinations thereof), with particularly emphasized examples being the increased resistance of the plant to animal and microbial pests such as insects, spiders, nematodes, mites, slugs, snails, etc., and furthermore, for example, the improvement of the plant's resistance to phytopathogenic fungi, bacteria and / or viruses by systemic acquired resistance, phytoalexins, elicitors, and the proteins and toxins expressed correspondingly, and the improved tolerance of the plant to specific herbicidal active compounds such as imidazolinones, sulfonylureas, glyphosate, phosphinothricin (such as the PAT gene), etc. The genes that impart the desired traits may also be present in combination with each other in the transgenic plant. Examples of transgenic plants that can be mentioned are important crop plants such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soybeans, potatoes, sugar beets, sugar cane, tomatoes, peas and other types of vegetables, cotton, tobacco, rape, and fruit plants (including fruit apples, pears, citrus fruits and grapes), with particular emphasis on maize, soybeans, wheat, rice, potatoes, cotton, sugar cane, tobacco and rape.Particularly emphasized traits are the increased resistance of plants to insects, spiders, nematodes, slugs and snails.

[0200] Crop protection - type of treatment Treatment of plants and plant parts with form A of the compound of formula (I) is carried out by customary treatment methods, for example, dipping, spraying, atomizing, irrigation, evaporation, dusting, spraying, broadcasting, foaming, coating, spreading, injection, watering (drenching), drip irrigation, and in the case of propagation material, in particular in the case of seeds, as a powder for dry seed treatment, a solution for liquid seed treatment, a water-soluble powder for slurry treatment, by seed coat treatment, coating by application one or more times, directly or in its vicinity, habitat, storage location. Furthermore, it is also possible to apply form A of the compound of formula (I) by the ultra-low volume method, or to inject the application form of form A of the compound of formula (I), or form A of the compound of formula (I) itself into the soil.

[0201] A preferred direct treatment of plants is foliar application, i.e., form A of the compound of formula (I) is applied to the foliage, where the treatment frequency and application rate should be adjusted according to the level of infestation by the pest in question.

[0202] In the case of a systemic active compound, form A of the compound of formula (I) also reaches the plant via the root system. The plant is then treated by the action of form A of the compound of formula (I) at the plant's habitat. This can be done, for example, by dipping or by mixing into the soil or nutrient solution, i.e., by impregnating the liquid form of form A of the compound of formula (I) into the plant's location (e.g., soil or hydroponic system), or by soil application, i.e., by introducing form A of the compound of formula (I) according to the invention in solid form (e.g., in the form of granules) into the plant's location, or by drip application (often also referred to as "chemigation"), i.e., by liquid application of form A of the compound of formula (I) according to the invention from a surface or subsurface drip line together with varying amounts of water at a specific location near the plant over a period of time. In the case of rice crops, this can also be done by metering form A of the compound of formula (I) in solid application form (e.g., as granules) into the flooded paddy field.

[0203] Seed treatment The control of animal pests by treating plant seeds has long been known and is the subject of ongoing improvement. However, seed treatment is associated with a series of problems that cannot always be solved in a satisfactory way. Therefore, it is desirable to develop methods for protecting seeds and germinating plants that eliminate or at least significantly reduce additional applications of pesticides during storage, after sowing, or after emergence of the plant. Furthermore, it is desirable to optimize the amount of active compound used so as to optimally protect seeds and germinating plants from attack by animal pests without damaging the plants themselves by the active compound used. In particular, seed treatment methods need to take into account the inherent insecticidal or nematicidal properties of genetically modified plants with pest resistance or pest tolerance in order to optimally protect seeds and germinating plants while minimizing the amount of pesticide used.

[0204] Accordingly, the present invention particularly also relates to a method for protecting seeds and germinating plants from attack by pests by treating the seeds with form A of the compound of formula (I). The method according to the invention for protecting seeds and germinating plants from attack by pests further comprises a method in which the seeds are treated simultaneously or successively in one operation with form A of the compound of formula (I) and a mixing component. The present invention also comprises a method of treating the seeds with form A of the compound of formula (I) and the mixing component at different times.

[0205] The present invention likewise relates to the use of form A of the compound of formula (I) for the treatment of seeds for protecting the seeds and the resulting plants from animal pests.

[0206] Furthermore, the present invention relates to seeds treated with form A of the compound of formula (I) according to the invention for protecting against animal pests. The present invention also relates to seeds treated simultaneously with form A of the compound of formula (I) and a mixing component. The present invention further relates to seeds treated at different times with form A of the compound of formula (I) and a mixing component. In the case of seeds treated at different times with form A of the compound of formula (I) and a mixing component, the individual substances may be present on the seeds in different layers. Here, the layers containing form A of the compound of formula (I) and the mixing component may optionally be separated by an intermediate layer. The present invention also relates to seeds on which form A of the compound of formula (I) and the mixing component are applied as components of a coating, or as a further layer, or as a further layer in addition to a coating.

[0207] Furthermore, the present invention relates to seeds which are subjected to a film coating process after treatment with form A of the compound of formula (I) in order to prevent dust abrasion on the seeds.

[0208] One of the advantages encountered in the systemically acting form A of the compound of formula (I) is the fact that by treating the seeds, not only the seeds themselves but also the plants obtained therefrom are protected from animal pests after germination. In this way, the immediate treatment of the crop at sowing time or immediately after sowing can be omitted.

[0209] It must be regarded as a further advantage that the germination and emergence of the treated seeds can be enhanced by treating the seeds with form A of the compound of formula (I).

[0210] Similarly, it is considered advantageous that form A of the compound of formula (I) can also be used, in particular, for transgenic seeds.

[0211] Furthermore, form A of the compound of formula (I) can be used in combination with compositions or compounds of signaling technology, for example, resulting in better colonization by symbiotic organisms such as rhizobia, mycorrhizal fungi and / or endophytic bacteria or fungi, and / or resulting in optimized nitrogen fixation.

[0212] Form A of the compound of formula (I) is suitable for protecting the seeds of any plant variety used in agriculture, greenhouses, forests or horticulture. In particular, this takes the form of seeds of cereals (e.g., wheat, barley, rye, millet and oats), maize, cotton, soybeans, rice, potatoes, sunflowers, coffee, tobacco, canola, rape, beets (e.g., sugar beets and fodder beets), peanuts, vegetables (e.g., tomatoes, cucumbers, legumes, brassicas, onions and lettuce), fruit plants, lawns and ornamental plants. The treatment of the seeds of cereals (e.g., wheat, barley, rye and oats), maize, soybeans, cotton, canola, rapeseed, vegetables and rice is of particular importance.

[0213] As already mentioned above, it is also particularly important to treat transgenic seeds with the compound of formula (I) in form A. This generally takes the form of seeds of plants containing at least one heterologous gene that generally controls the expression of polypeptides having pesticidal and / or nematicidal properties. The heterologous genes in transgenic seeds are derived from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. The present invention is particularly suitable for the treatment of transgenic seeds containing at least one heterologous gene derived from a Bacillus sp. Particularly preferably, it is a heterologous gene derived from Bacillus thuringiensis.

[0214] In respect of the present invention, the compound of formula (I) in form A is applied to the seeds. Preferably, the seeds are treated in a state that is stable enough to avoid damage during the treatment. Generally, the seeds can be treated at any point in time between harvesting and sowing. The seeds that are usually used are separated from the plant and do not contain cobs, husks, stems, outer skins, hairs or fruit pulp. For example, it is possible to use seeds that have been harvested, washed and dried to a water content that allows storage. Alternatively, it is also possible to use seeds that have been treated, for example, with water after drying and then dried again, for example primed seeds. In the case of rice seeds, for example, seeds soaked in water can be used at a specific stage of the rice embryo (the "pigeon breast stage"), which stimulates germination and promotes more uniform emergence.

[0215] The seed dressing formulations that can be used according to the present invention can be used to treat a wide variety of different types of seeds, either directly or after pre-dilution with water. For example, the concentrates or preparations obtained by dilution with water can be used to dress the seeds of cereals such as wheat, barley, rye, oats, and triticale, as well as corn, rice, rape, peas, beans, cotton, sunflower, soybean, and beet, or the seeds of a wide variety of different plant species. The seed dressing formulations that can be used according to the present invention, or their diluted use forms, can also be used to dress the seeds of transgenic plants.

[0216] For the treatment of seeds with the seed dressing formulations that can be used according to the present invention, or the use forms prepared therefrom by adding water, all mixing units that can be conventionally used for seed dressing are useful. Specifically, the procedure in seed dressing is to put the seeds into a mixer, operate batchwise or continuously, add a specific desired amount of the seed dressing formulation, for example, as it is or after pre-dilution with water, and mix everything until the formulation is uniformly distributed on the seeds and the excess moisture evaporates.

[0217] The application rate of the seed dressing formulations that can be used according to the present invention can be varied within a relatively wide range. It is induced by the specific content of Form A of the compound of formula (I) in the formulation and the seeds. The application rate is generally 0.001 - 50 g per kilogram of seeds, preferably 0.01 - 15 g per kilogram of seeds.

Examples

[0218] Table 8 Materials used in the examples Dispersant

Table 8

[0219] Rheology agent

Table 9

[0220] pH buffer / antifoaming agent / bactericide / antifreeze / antioxidant

Table 10

[0221] Tests and methods used in the examples Method All data that is part of this application has been created according to the methods described below, unless otherwise indicated. The samples used for the measurements were used directly without further sample preparation.

[0222] XRPD X-ray diffraction patterns were recorded at room temperature using an XRD diffractometer X`Pert PRO (PANalytical) and a STOE STADI-P (Cu Kα1, wavelength 1.5406 Å). All X-ray reflections are presented as °2Θ (theta) values (maximum peak) with a resolution of ±0.2°.

[0223] Raman Raman spectra were recorded at room temperature using an FT-Raman spectrometer (models RFS100 and MultiRam) from Bruker. The resolution was 2 cm -1 . The measurements were performed in glass vials or aluminum disks.

[0224] IR IR-ATR spectra were recorded at room temperature using an FT-IR spectrometer Tensor37 equipped with a universal diamond ATR device or a Lumos equipped with an ATR device from Bruker. The resolution was 2 cm -1 .

[0225] DSC The DSC thermograms were recorded using a DSC calorimeter DSC3 or DSC3+ from Mettler or Diamond DSC and DSC8000 from Perkin Elmer. Measurements were carried out using perforated aluminum pans at a heating rate of 20 K min -1 or 2 K min -1 . The flow gas was nitrogen. Examples I Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one I.1 Preparation of polymorphic Form A Example 1 430 mg of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one prepared as described in International Publication No. WO 2011 / 051151 was dissolved in 60 ml of toluene, and the solution was filtered. One-fourth of the solution was stored at room temperature and ambient humidity until the solvent had evaporated. The residue was tested by thermal analysis and corresponded to the title compound of polymorphic form A.

[0226] Example 2 404 mg of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one prepared as described in International Publication No. WO 2011 / 051151 was dissolved in 60 ml of methanol, and the solution was filtered. One-fourth of the solution was stored in a refrigerator until the solvent had evaporated. The residue was tested by thermal analysis and corresponded to the title compound of polymorphic form A.

[0227] Example 3 405 mg of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one prepared as described in International Publication No. WO 2011 / 051151 was dissolved in 20 ml of ethyl acetate, and the solution was filtered. 5 ml of n-heptane was added to one-fourth of the solution, and this was stored at room temperature and ambient humidity until the solvent had evaporated. The residue was tested by X-ray diffraction and corresponded to the title compound of polymorphic form A.

[0228] Example 4 413 mg of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one prepared as described in International Publication No. 2011 / 051151 was dissolved in 60 ml of isopropanol, and the solution was filtered. One-fourth of the solution was stored at room temperature and ambient humidity until the solvent evaporated. The residue was viscous. It was scratched and left at room temperature and ambient conditions until crystallization occurred. The residue was tested by X-ray diffraction and corresponded to the title compound of polymorphic form A.

[0229] Example 5 106 mg of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one prepared as described in International Publication No. 2011 / 051151 was suspended in 1 ml of water and shaken at 25 °C (1400 rpm, 30 minutes shaking / 30 minutes stopping) in an Eppendorf Thermomix. After one week, the suspension was dried at room temperature and ambient humidity. The residue was tested by IR spectroscopy and corresponded to the title compound of polymorphic form A.

[0230] II Polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one II.1 Preparation of polymorphic Form B Polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one was prepared as described in Production Example 3 of International Publication No. 2011 / 051151.

[0231] III. Water solubility of flupyradifurone polymorphs The water solubility of FPF polymorphs A and B was determined by saturating a specific amount of deionized water with each polymorph, stirring the resulting saturated suspension overnight, filtering the undissolved solid residue, and measuring the dissolved concentration of FPF in the filtrate.

[0232] Table 9: Measured water solubility of the FPF polymorph

Table 11

[0233] IV Full Pyraziflumid FS 480 Formulation Example IV.1 Preparation of Full Pyraziflumid FS 480 Weigh the formulation components, homogenize them with a high-shear device (e.g., Ultraturrax or colloid mill), and then grind them in a bead mill (e.g., Dispermat SL50, 80% filling, 1.0 - 1.25 mm glass or zirconium oxide beads, 4000 rpm, circulating grinding) until a particle size of <10 μm is achieved.

[0234] Alternatively, mix the formulation components in a bottle, and then add approximately 25% by volume of 1.0 - 1.25 mm glass beads. Then, close the bottle, clamp it in a stirrer (e.g., Retsch MM301), and process it at 30 Hz for several minutes until a particle size of <10 μm is achieved.

[0235] After grinding to the required particle size distribution, add 0.16% by weight of a thickener (e.g., xanthan gum), and a biocide, as well as an antifoaming agent and water to obtain a fine active substance suspension. Add water in an amount such that the total amount is 100% by weight. Dilution with water gives a stable suspension of the active substance.

[0236] Table 10 : Composition of Full Pyraziflumid FS 480

Table 12

[0237] IV.2 Morphology Control of Full Pyraziflumid during Grinding Table 11 : Morphology of Full Pyraziflumid as a Function of Grinding Conditions of Full Pyraziflumid FS 480

Table 13

[0238] IV.3 Method for Measuring the Stability of Different Polymorphs of Full Pyrazifluone in FS 480 Storage stability The test is carried out for a predetermined number of weeks (w) at different temperatures such as 0 °C, 20 °C, 30 °C, 40 °C, 54 °C, or in a thaw-freeze cycle (= TW; a constant temperature change from -15 °C to +30 °C and back within one week).

[0239] Immediately after storage Phase separation is reported as the precipitate fraction and is calculated from the value obtained by dividing H1 [the level of the interfacial layer between the precipitate phase and the supernatant] by H0 [the total filling height of the sample], or, as in the case of this application, is calculated as the supernatant fraction: Precipitate fraction = (H1 / H0) × 100 [%] or Supernatant fraction = 100 - precipitate content [%] A stable and convenient formulation is expected to show no or only slight phase separation during long-term storage at high temperatures and to be easily re-homogenized. If significant phase separation is observed after a short storage time, the storage stability is limited, and there is a significant tendency for it to be difficult to disperse during storage or for a non-dispersing precipitate to form.

[0240] In some cases, the stability is catastrophically lost, the formulation hardens, and the formulation may become unusable.

[0241] Table 12 : Stability of Full Pyrazifluone FS 480 by Form B

Table 14

[0242] Table 13 : Stability of Full Pyrazifluone FS 480 with Form A

Table 15

[0243] Comments on Tables 12 and 13 As can be seen from the data in Tables 12 and 13, samples containing some amount of Form B of full pyraclostrobin after grinding (more than 90%) are not stable during storage at high temperatures, rendering the formulation unusable and completely solidifying.

[0244] Mixtures of Form A and Form B of full pyraclostrobin can be converted to only Form A, or mostly Form A, during grinding, and these formulations containing only Form A of full pyraclostrobin, or a large amount of Form A, are stable upon storage at 40 °C for 4 weeks, and some at 54 °C for 4 weeks.

[0245] In other words, the dispersion formulations composed mostly of Form A of full pyraclostrobin are compatible with high-temperature storage conditions, and surprisingly, are more stable against storage, and this feature makes these formulations much more reliable and usable.

[0246] Biological test of V full pyraclostrobin (FPF) FS 480 Physicochemical properties are important factors for systemic plant uptake and biological activity. To test the effectiveness of various FPF modifications against the bird cherry-oat aphid (Rhopalosiphum padi), a sufficient number of barley seeds (cultivar "Scarlett", 1000-grain weight: 43.6 g) were manually dressed with a specified amount of flupyradifurone FS 480 formulated in 100% form A, 100% form B, and a combination of 99% form A and 1% form B, respectively. The test concentrations were 0.15 g of active ingredient per kg of seeds (commercial dosage ratio in cereals) and 0.075 g of active ingredient per kg of seeds. Vertical boxes were filled with 5,900 g of sandy loam soil (75.1% sand, 10.3% clay, 14.8% silt, 1.75% humus, pH 6.9), and 15 seeds per box were sown at an interval of approximately 2.5 cm and a depth of 3 cm. After sowing, the boxes were watered to reach 50 - 70% of field capacity and covered with plastic foil until the first plants emerged. Aphid infestation was carried out at the second leaf stage by adding multiple fragments of infested leaf material to each test box. The second reinfestation was carried out 3 days after the first infestation using the aforementioned method. The biological activity of the FPF modifications tested was evaluated by visual assessment of the colonized leaf area 3 days and 7 days after the first infestation, compared to untreated and infested controls. The results were expressed as a percentage of efficacy. 100% efficacy means that aphids could not form a population, and 0% means that aphids colonized an equivalent leaf area to the untreated infested check. The growth conditions were a constant temperature of 20°C, a relative humidity of 50%, and 14 hours of lighting using a sodium pressure lamp. The experiment included 3 replicates per treatment. The results are shown in Table 14.

[0247] Table 14: Systemic Biological Efficacy of FPF FS 480 Formulated with FPF Forms A and B (Test Report SGRS040)

Table 16

[0248] Comments on Table 14 The FPF concentrates tested showed excellent efficacy against the cereal leaf beetle (R. padi) after seed treatment. In particular, no difference was observed between half (0.075 g / kg) and full dose (0.15 g / kg) at the first evaluation date. However, as expected, 0.15 g / kg produced excellent residual activity. Interestingly, no differences in biological activity were observed between the individual FPF modifications. This result is surprising since the systemic biological efficacy of the chemical active ingredient is closely related to its water solubility. The results of this experiment clearly show that even when the water solubility of FPF Form A is reduced by 60%, its biological efficacy does not decrease compared to FPF Form B. This form is also particularly easy to use in combination with the fact that it is significantly more stable as an FS formulation.

Claims

1. Formula (1) 【Chemistry 1】 A pesticide formulation comprising crystalline form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, wherein the X-ray powder diffraction pattern at 25°C and under Cu-Kα1 radiation shows at least three characteristic reflections listed as the following 2Θ values ​​±0.2°: 15,0; 20,1; 21,0; 22,4; 29,4; 33,1 and 33,2, and at least 85% by weight of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1) is present in its crystalline form A.

2. The pesticide formulation according to claim 1, wherein at least 95% by weight of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1) is present in its crystalline form A.

3. a) Polymorph A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, b) One or more dispersants, c) One or more rheological control agents (rheological modifiers), and h) Carrier (filler) up to 1 liter A pesticide formulation according to claim 1 or 2, comprising:

4. a) Polymorph A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, b) One or more dispersants, c) One or more rheology control agents (rheology modifiers), d) One or more pH buffers, e) One or more defoaming agents, f) One or more biocides, g) One or more antifreeze agents, and h) Carrier (filler) up to 1 liter A pesticide formulation according to claim 1 or 2, comprising:

5. a) in a concentration range of 400 to 500 g / L, b) in a concentration range of 60 to 80 g / L, c) in a concentration range of 6 to 10 g / L, and h) Up to 1L of water A pesticide formulation according to claim 3, including the above.

6. a) in a concentration range of 400 to 500 g / L, b) in a concentration range of 60 to 80 g / L, c) in a concentration range of 6 to 10 g / L, d) in a concentration range of 0.01 to 10 g / L, e) in a concentration range of 0.1 to 2 g / L, f) in a concentration range of 0.1 to 3 g / L, g) in a concentration range of 10 to 100 g / L, and h) Up to 1 liter of water The pesticide formulation according to claim 4, including the above.

7. The pesticide formulation according to claim 1 or 2, comprising one or more further adjuvants and auxiliaries as component i).

8. The pesticide formulation according to claim 1 or 2, comprising one or more further active ingredients k).

9. A pesticide formulation according to claim 1 or 2 for use as a seed coating.

10. A method for producing the crystalline form [A] of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, comprising the following steps: a) Diluting and / or suspending the compound of formula (1) in a suitable solvent or solvent mixture; b) A step of adjusting the temperature to 0 to 25°C; and c) A step of storing the solution or slurry obtained in step b) at a temperature of 0 to 25°C until the solvent evaporates and crystals of polymorph A are formed. A manufacturing method that includes this.

11. The method according to claim 10, wherein the solvent is selected from the group consisting of toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol, or water.

12. The method according to claim 10, wherein the solvent is selected from the group consisting of toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol, or water.

13. A method for producing the crystalline form [A] of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one by grinding the crystalline form [B] or a mixture of [A] and [B] in a bead mill using glass or zirconium oxide beads.

14. Equation (1) for crystal form A 【Chemistry 1】 A compound of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, A compound that exhibits characteristic reflections in X-ray powder diffraction patterns at 25°C and under Cu-Kα1 radiation, with at least the following 2Θ values ​​±0.2°: 15,0; 20,1; 21,0; 22,4 and 29,4.

15. In the X-ray powder diffraction pattern at 25°C and under Cu-Kα1 radiation, characteristic reflections were observed, listed below as 2Θ values ​​±0.2°: 15,0; 20,1; 21,0; 22,4; 29,4; 33,1 and 33,2. Here, the Raman spectrum shows at least the following bands (cm -1 Maximum peaks at: 111, 880 and 1711. The IR spectrum includes at least the following bands (cm -1 Maximum peaks in: 809, 1071 and 1597, The compound according to claim 14.

16. Use of the compound according to claim 14 or 15 for the manufacture of a pesticide formulation having improved storage stability.

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